Process of dyeing with basic dyes.



Nrrne STATES MAX BEOKE AND HERMANN BABLIOH, OF HDOHST-ON-THE-MAIN, GER- MANY, ASSIGNORS TO THE FARBWERKE, VORMALS MEISTER, LUGIUS & BRUNING, OF SAME PLACE.

PROCESS OF DYEING WITH BASIC DYES.

SPECIFICATION forming part of Letters Patent No. 666,256, dated January 22, 1901.

Application filed August 5, 1397- Serial No. 647,219. (Specimens) To all whom it may concern.-

Be it known that we, MAX BEGKE, chemist, and HERMANN BABLICH, chemist, citizens of the Empire of Austria-l lungary, residing at l lochst-on-the-Main, in the Empire of Germany, have invented a new and useful Improvement in Dyeing Fast Tannin-Antimony Lakes of Polyazo Dyestuffs and Basic Safra- 11in Azo Dyestuffs on Vegetable Fiber, (for which Letters Patent were granted to us in France, No. 264,692, dated March 5, 1897, and in England, No. 5,259, dated February 26, 1897,) of which the following is a specification.

It is a well-known fact that the fixing of basic dyestuffs on materials made of vegetable fibers demands the troublesome three-bath systemnamely, first mordanting in the tannic bath, then fixing in a bath containing a salt of antimony, and finally dyeing. The inconvenience of this method-a bundle of yarn, for instance, requiring on the average five hours work, besides immersion over night in the tannin mordantand the heavy costs connected therewith, increased by the expense of maintaining a large plant of vats, were the causes that the application of fast basic dyestuffs was neglected for many purposes and that the less fast, but simpler, and consequently cheaper, directly-acting dyestu ifs were employed.

We have succeeded in finding a new method suitable for the purposes of cotton dyeing and applicable to a large group of basic dyestuffs, particularly basic polyazo dyestuffs, having as component aromatic amidoammonium bases or amidobenzylamin or their derivatives and such basic monoazo dyestuffs deriving from diazo safranins. This method constitutes a great technical progress by its simplicity and easy working, on the one hand, and by the fastness of the tints thus obtained, on the other hand. We have, in fact, discovered that the said basic azo dyestuffs may be directly fixed on the vegetable fiber with out mordant if the fiber be treated in neutral or slightly-acid baths, preferably with an addition of neutral salts, such as common or Glaubers salt, together with the solution of the dyestuffs at a warm temperature or, still better, at the boil, and that the dyed colors may be transformed on the fiber by a subsequent treatment with solutions of tannins and antimony salts or mixtures of both in the dye fluids themselves or in a second bath into their very fast tannin-antimony lakes. This transformation not only takes place if the fiber dyed with the basic coloring-matter be treated in one or two separate baths, first with tannin and then with antimony solutions; but it also takes place in the same bath if the dyeing be done in presence of an antimony salt followed by treatment with tannin. It is likewise the case in the same or in a second bath if the subsequent treatment is carried outwith mixtures of tannin and antimony-salt solutions containing for the most part insoluble tannate of antimony. It is remarkable that in this latter case the best results as regards even dyeing and fastness are obtained.

The affinity to the fiber is evidently so great that the tannate of antimony of the bath not only does not withdraw the coloring-matters, but, on the contrary, is itself withdrawn from the bath by the dyestufis in the fiber which are not yet fast, thus forming the fast tanninantimony dyestuif lake on the fiber. This formation of lakes on the fiber is not only easier according to this new method than by the old one, as one, or at the most two baths only are necessary instead of three and which can both be further used for boiling, but this formation of lakes is also more complete than that by the old method, producing much faster and more-evenly dyed tints, an importance not to be underrated in'the cases of firm twisted yarns, threads, and close tissues.

hen using alkaline water of factories sufficient acetic, sulfuric, or hydrochloric, &c., acids must be added to the dye fluid, so as to avoid formation of the badly-actin g dye bases. This new method is found to be applicable to all such strong basic disazo dyestuffs as contain as first component a diazotizable am monium base (metaand paraamidophenyl-trialkylammonium, paramethyl-ortho-amidophenyltrialkylammonium) or amidobenzyl amin or its alkyl derivatives (paraand orthoamidobenzyl-dialkylamin, amidobenzyltrialkylammonium) in middle position, a further diazotizable amin (alpha-naphthylamin amidonaphtholethyl and methylether, para-xylidin, symmetrical meta-xylidin, meta-toluidin, meta-chloranilin, ortho-anisidin, orthophenetidin, ortho amido para cresol alkyl ether,para-chloro-meta-toluidin, &c.,) in final position, a not-sulfonated amin or phenol capable of being combined (phenol, alphaand beta-naphthol,amidonaphthols,dialkyl-metaamidophenols and naphthols, meta-phenylene and toluylene-diamin chrysoidin, pyrazolene) as well as such basic' disazo dyestuffs resulting from the action of amidoazo bodies upon 2.7 oxynaphthalin-trialkylammonium, and finally such monoazo dyestuffs as result from the action of diazosafranins (also alkylated) upon alphaand betanaphthol, dioxynaphthalin, phenol, dimethyland diethyl-anilin, dimethyl and diethyl-meta-amidophenol, amido-naphthols, alkylamido-naphthols, alphanaphthylamin, toluylene diamin and phenyl enediamin.

The new method,which is limited to a group of strong basic azo dyestuifs, is based upon the fact hitherto unknown and newly-discovered by usthat the aifinity of these dyestuffs to the vegetable fiber is greater than the inclination to form tannin-antimony lakes. Just the reverse is the case with most of the basic dyestuffs hitherto introduced in the dyeing industry. Their afiinity to the vegetable fiber is so weak that even when applied to the fiber by means of padding they are extracted from the fiber by a subsequent treatment of tannin, applicable in the case of silk instead of adhering to it.

The new method has opened a new field for the practical fixing on the fiber of a large group of fast basic dyestuffs, involving a "cry important technical progress with regard to the saving of steam, wages, and amortization of the plant, the length of time, (two to two and one-half hours, as a rule, suffice for one lot,) and the better dyeing obtained as well as greater fastness compared to the process of previously mordanting hitherto employed. This great technical improvement is applicable to all modifications of the method even when working according to the separate-bath system, as the using again of the dye and mordant fluids also permits a further application of the heat therein contained in contrast to the three-bath system, and all other advantages above mentioned assert themselves in the fullest degree.

The following illustrates the mode of working:

First. Red on twenty kilos of loose cotton.

The well-boiled cotton is introd uced into a hot .tized meta-amidotrimethylphenylam moniu m with meta-toluidin by further diazotizing and combining with beta-naphthol. The cotton is worked at the boil for one hour, then taken out, eight hundred grams of tannin and one kilo of acetic acid are added, the cotton is diamin is worked for one hour at the boil.-

The yarn is taken out and wrung and introduced into the second boiling-bath, prepared with five hundred liters of water, one kilo of acetic acid, the decoction of five kilos of sumacin leaves, and four hundred grams of tartar emetic (or the equivalent quantity of oxalate of antimony or antimony salt.) The yarn is boiled and well worked in this bath for one-half hour, then taken out,washed, and dried. A dark indigo-like very fast navyblue results. Both baths may serve again for the next lots.

Third. Green on twenty kilos cotton sateen- The well-boiled sateen is dyed in about threefourths of an hour on a jigger in about two hundred liters of water with four kilos of common salt, four hundred grams of the dyestuif from diazodiethylsafranin or dimethylanilin, and one hundred grams of the disazo dyestufi": from meta-amidotrimethylphenylam monium, ortho-ch loro-meta-tol uidin and in ethyl phenylpyrazolone, to which are then added one kilo of acetic acid and the solution of eight hundred grams of tannin and four hundred grams of tartar emetic and boiled for another threefourths of an hour.

Having thus described our invention, we claim as new and desire to protect by Letters Patent 1. The herein-described process for dyeing fast tannin-antimony lakes of basic polyazo dyestufls and basic safraninazo dyestuffs on vegetable fiber, which consists in first dyeing these dyestuifs directly upon 'thevegetable fiber and then converting them by subsequent treatment with tannin and antimony salts into the fast tannin -antimony lakes, substantially as set forth.

2. The herein-described process of dyeing vegetable fiber by basic polyazo and safraninazo dyestuffs, which consists in first dyeing these dyestuffs in a neutral or slightlyacid bath directly upon the vegetable fiber, and then converting them by subsequent treatment with tannin and an antimony salt into the fast tannin-antimony lakes, substantially as set forth.

In testimony that we claim the foregoing as our invention we have signed our names in presence of two subscribing witnesses.

MAX BEOKE. HERMANN BABLICH. WVitnesses:

HEINRICH HAHN, ALFRED BRIsBoIs. 

